Trisazo-dyestuffs and process of making same



Patented Feb. 13, 1945 UNITED STATES PATENT OFFICE TRISAZO-D-YE STU FFS AND PROCESS OF MAKING SAME Walter Anderau, Basel, Switzerland, assignor to Society of Chemical Industry'in Switzerland Basle, Basel,

No Drawing. Application April 1, 1942, Serial No.

- 437,282. In Switzerland April 3,1941

v I I i 11 Claims. It has been found that valuable trisazo-dye-- stufis can be obtained by coupling one mol. of the diazo compound of an ammoazo-dyestufi of the general composition HOOC wherein R stands for an aryl radical containing the hydroxy and carboxylic acid groups inorthoposition to one another, .1: stands for an alkyl or alkoxy group and y stands for an alkoxy group, with one mol. of 5:5'-dihydroXy-2:2-dinaphthylam'ine-"l:'7-disulfonic acid, and then uniting one mol. of the diazo-dyestufi thus obtained with one mol. of the diazo compound of an 'arylamine of the general formula wherein a: and y have the meaning given above.

The same dyestuffs are obtained by coupling' first of all one mol. of the diazo-compound of an arylamine of the general formula wherein a: and y have the above. given significance, with one mol. of :5"-dihydroxy-2:2'-dinaphthylamine-l:7'-disulfonic acid and then coupling one mol. of the inonoazo-dyestufi? thus obtained with one mol.'of the diazo compound'of an aminoazo-dyestufi'of the general-composition wherein R, :t and y have the meaning indicated above.

As diazo components for the construction of the monoazo-dyestuff containing the. salicyclic acid group may be used, for example, 2-hydroxy- S-amino-l-benzoic acid or 2-hydroxy-3-aminol-benzoic acid, and as aim-component the 1- amino-2-alkoxy-5-alkylor -5"-alkoxy-benz'enes wherein the alkyl and alkoxy groups may contain one, two or more carbon atoms, but preferably not more than three. Such azo-compocarbonatasodium bicarbonate or ammonia.

The dyestuffs obtained by the present process dye cellulose fibers, such as cotton, linen, ramie,

hemp, jute, etc. or fibrous materials from regenerated cellulose, such as viscose and copper rayon, as well as films, ribbons and similar articles from regenerated cellulose, chiefly reddish blue tints.

Particularly valuable dyeings which are fast towashings are obtained if the dyeings are after-- treated with agents yielding copper.

The treatment of the cellulose fibers dyed with 1 the dyestuffs of the above composition in usual manner from a neutral or feebly alkaline bath, for instance alkaline with sodium carbonate, with agents yielding copper may be carried out with ordinary copper salts, such as copper sulfate, in

a neutral or feebly acetic acid bath, or preferably with copper compounds stable towards alkalies, such as are obtained for example by the reaction of ordinary copper salts with aliphatic hydroxycarboxylic acids, such as tartaric acid, in an alkaline agent, for example an agent alkline with alkali carbonate. Dyeing processes in which such coppering agents are used have been described for example in U. S. Patents 2,148,659 and 2,185,905. The treatment with the agents yielding copper may be effected in the dyebath or in a fresh bath.

The following example illustrates the invention,

the parts being .by weight:

3 parts of 4-amino-2-inethyl-5-methoxy-4'-hydroxy-S -carboxy- 1' 1 .-azobensene are diazotized in usual manner and cou'pledwith 4:6 parts of 5:5 -dihydroxy-2 2 -dinaphthylamine-7 7-disulionic acid in a solutionalkaline with sodium carbonate, while poolingi The dyestuff formed is salted out, filtered, dissolved in water with addition of sodium carbonate, and the solution is cou- ;pled, after addition of some ice, with the diazo compound prepared from 1.3 parts of 1-amino-2- methoxy-5-methyl-benzene. When coupling is 3. Process for the manufacture of azo-dyecomplete, the dyestuff of the probable formula stuffs, comprising coupling 5:5-dihydroxy-2:2

. H0 s soin 33; 3 NH- CH;

0 0 OH 0 0 H3 H H 0 H;

is salted out by addition of common salt, filtered 1 dinapht yl min 7r' i l nic a on h n and dried. It is a dark powder of bronze appear- 0 hand, with ta diazotized aminoazo-dyestuff of the ance which dissolves in concentrated sulfuric acid al OI HIa to a greenish blue solution, in water to a violet H0 11 solution and dyes cotton reddish blue tints which, when treated with copper salts, become more greenish and are fast to washing and light. 15 H006 a A very similar dyestuff of somewhat greener 1/ ti t is obtained by using 4..amjno '2;5 dimethoxywherein R stands for a benzene radical contain- 4'-hydroxy-3-carboxy-1:1-azobenzene as :first ins thehydroxyl and carboxyl gro ps in orthoidiazo component and 1-amino-2z5-dimethoxyposition o e a t er, and ,y stands for an benzene or i1-'amino-2 methoxy-5 methylbenzene y p ngup to'three carbon atoms, a second diazo component, and, onthe otherhan'dywith *a-diazotized amine What I claim i of th 'generalformula l. 'Process for the manufacture of azo-dye- "stuffs, comprising coupling 5:=5'- dihydroxy-2:2'-

dinaphthYlamine-l 7'-disulfonic acid, on the one hand,'with a diazotized aminoazo-dyestu'ff of the general formula 1/ HO wherein y has the same meaning as given above.

I 4. iProcess for the manufacture of azo-dyestuffs, comprising coupling :5::5"-:dihydroxy-2:2- 0 0 dinaphthylamineflz7edisulfonic acid, 'on'the one 1 hand, with .at diazotized amine of :the "formula wherein R stands fora benzene'radical containon, ing the 'hydroxyl and carboxyl groups in orthoas position to oneianother, 4:1: stands "for 'a member HOON fN ;NH2 of the group consisting of alkyl and alkoxy -groups containing up to three carbon atoms, and 1 stands H00, ogcn,

for an alkoxy group containing uptto three carbon and, on the other hand, with a diazotized amine atoms, and, on the otherlhand, with a diazotized 40 of the formula amine of the general formula v 0H:

1/ "5. Process for the manufacture of azo-dyewherein a: and 1/ have thesame meaning aszgiven "stuffs, comprising coupling 5:5-dihydroxy-J2:2- above. v dinaphthylamine l":fl' dislilfonicacid,'on the one 2. Process for the manufacture of azo-dyehand, with a diazotized amine of the formula stuffs, comprising coupling 5:15'-.dihydroxy-2:2'- 5O 00m dinaphthylamine-7:7-'disulfonic acid, 'onthe one "hand, with a diazotized aminoazo-dyestufiof the HO N= NH;

general formula CH: H0O OH:

' and, 'on'the other' han'd, with a diazotizedamine I RN=N -NH: of the formula HO O C' 0 CH:

1/ wherein. R stands for a benzene radical containing the hydroxyl and carboxylgroups in orthoposition to one another, and '1; stands for an m CH: alkoxy group containing up to three'carbonatoms, 6. Azo-dyestufis of the general "formula H03 S. /S 01H 1 -7NH I o .1 1

none" 1! OH OH y "and, on the 'Othefhand, with diazotized amine wherein 'Ristands .forwa 'benzene.radical ..containof the general formula ving the hydroxyl and icarboxyl groupsiin ortho- 0 position to one another, mistands .for amember of the group consisting of .alkyl and :alkoxy groups :containing up to three ,carbonzatoms and Ky stands for an alkoxy groupucontaining up to wherein 3 has the same meaning'as given above. 19111 99 10a! boll 'NHi 7. Azo-dyestuffsof the general formula 1' 1 wherein R stands for a benzene radical containing the hydroxyl and carboxyl groups in orthoposition to one another, and y stands for an alkoxy group containing up to three carbon 7 atoms.

8. Azo-dyestufis of the general formula 7 H0 38 NH 08 RN=N N= N=N v H O O C 7 11 H H v wherein R stands for a benzene radical containa N: M

' Gas 7 I M O OH CH:

ing the hydroxyl and carboxyl groups in'orthoposition to one another, and y stands for an alkoxy group containing up to three carbon atoms.

9: The azo-dyestufi of the formula on, 1103s "NH' s on1 on" cool: OCH; H

10. The azo-dyestufi of the formula OCH CH:

11. The azo-dyestuff of the formula 0 CH3 H 

